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钴、镍和铜与α-烷基甘氨酸盐形成的配位化合物的结构多样性:固态晶体学和电子自旋共振研究

Structural diversity in the coordination compounds of cobalt, nickel and copper with -alkylglycinates: crystallographic and ESR study in the solid state.

作者信息

Vušak Darko, Smrečki Neven, Muratović Senada, Žilić Dijana, Prugovečki Biserka, Matković-Čalogović Dubravka

机构信息

Department of Chemistry, Faculty of Science, University of Zagreb Horvatovac 102a HR-10000 Zagreb Croatia

Laboratory for Magnetic Resonances, Division of Physical Chemistry, Ruđer Bošković Institute Bijenička 54 HR-10000 Zagreb Croatia.

出版信息

RSC Adv. 2021 Jul 6;11(38):23779-23790. doi: 10.1039/d1ra04219j. eCollection 2021 Jul 1.

Abstract

Reactions of -methylglycine (HMeGly), -ethylglycine-hydrochloride (HEtGlyCl) and -propylglycine-hydrochloride (HPrGlyCl) with cobalt(ii), nickel(ii) and copper(ii) ions in aqueous solutions resulted in ten new coordination compounds [Co(MeGly)(HO)] (1), [{Co(MeGly)}(μ-OH)]·2HO (1d), [Cu(MeGly)(HO)] (2α), [Co(EtGly)(HO)] (3), [Ni(EtGly)(HO)] (4), [Cu(μ-EtGly)] (5p), [Co(PrGly)(HO)] (6), [Ni(PrGly)(HO)] (7), and two polymorphs of [Cu(PrGly)(HO)] (8α and 8β). Compounds were characterized by single-crystal and powder X-ray diffraction, infrared spectroscopy, thermal analysis and X-band electron spin resonance (ESR) spectroscopy. These studies revealed a wide range of structural types including monomeric, dimeric and polymeric architectures, as well as different polymorphs. In all monomeric compounds, except 2α, and in the coordination polymer 5p hydrogen bonds interconnect the molecules into 2D layers with the alkyl chain pointing outward of the layer. In 2α and in the dimeric compound 1d hydrogen bonds link the molecules into 3D structures. 1d with cobalt(iii), and 4 and 7 with nickel(ii) are ESR silent. The ESR spectra of 1, 3 and 6 are characteristic for paramagnetic high-spin cobalt(ii). The ESR spectra of all copper(ii) coordination compounds show that the unpaired copper electron is located in the d orbital, being in agreement with the elongated octahedral geometry.

摘要

在水溶液中,α-甲基甘氨酸(HMeGly)、α-乙基甘氨酸盐酸盐(HEtGlyCl)和α-丙基甘氨酸盐酸盐(HPrGlyCl)与钴(II)、镍(II)和铜(II)离子反应生成了十种新的配位化合物:[Co(MeGly)(H₂O)₄](1)、[{Co(MeGly)}₂(μ-OH)]·2H₂O(1d)、[Cu(MeGly)(H₂O)₄](2α)、[Co(EtGly)(H₂O)₄](3)、[Ni(EtGly)(H₂O)₄](4)、[Cu(μ-EtGly)]₂ (5p)、[Co(PrGly)(H₂O)₄](6)、[Ni(PrGly)(H₂O)₄](7)以及[Cu(PrGly)(H₂O)₄]的两种多晶型物(8α和8β)。通过单晶和粉末X射线衍射、红外光谱、热分析以及X波段电子自旋共振(ESR)光谱对这些化合物进行了表征。这些研究揭示了广泛的结构类型,包括单体、二聚体和聚合物结构,以及不同的多晶型物。在所有单体化合物中,除了2α,以及在配位聚合物5p中,氢键将分子连接成二维层,烷基链指向层外。在2α和二聚体化合物1d中,氢键将分子连接成三维结构。1d中的钴(III)以及4和7中的镍(II)是ESR沉默的。1、3和6的ESR光谱是顺磁性高自旋钴(II)所特有的。所有铜(II)配位化合物的ESR光谱表明,未成对的铜电子位于d轨道,这与拉长的八面体几何结构一致。

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